Search results for "Vibrational spectroscopy"
showing 10 items of 85 documents
Quasirelativistic transition property calculations by the intermediate Hamiltonian method: Electronic transition dipole moments and radiative lifetim…
2001
We present a quasirelativistic method of ab initio calculations on molecular excited states and electronic transition moments within the relativistic effective potential approximation, based on the construction of intermediate Hamiltonians and spin-free one-particle transition density matrices by means of the many-body multipartitioning perturbation theory. The method is applied to describe the electronic transitions involved in the radiative decay of the ${A0}_{u}^{+},$ ${B0}_{u}^{+},$ and ${B1}_{u}$ states of ${\mathrm{Te}}_{2}.$ Good agreement of the computed transition dipole moment functions with their empirical counterparts is achieved. Theoretical radiative lifetime estimates for sev…
top data system (TDS) software for spectrum simulation of asymmetric molecules
2005
Abstract The D 2 h TDS ( D 2 h Top Data System) program suite has been developed with the aim of studying any rovibrational band or polyad of X 2 Y 4 ( D 2 h ) asymmetric top molecules. It is based on the same principles as similar programs from our group already released for various molecular symmetries ( T d , O h , C 4 v , C 2 v ). We work in the O ( 3 ) ⊃ D 2 h chain and this choice has consequences on the method used to specify the input parameters of the programs for Hamiltonian and transition moment calculations. Two examples concerning the ν 12 and ν 2 bands of the C 2 H 4 molecule are presented. This suite consists of a series of FORTRAN programs called by a script. The whole packa…
State-selective chirped adiabatic passage on dynamically laser-aligned molecules
2005
We show that rovibrational state selectivity can be achieved by chirped adiabatic passage of molecules that are adiabatically aligned by a nonresonant laser field. We develop the tools to design the appropriate frequency and amplitude modulations that allow us to select a given route in the Hilbert space that leads to a final complete excitation of the chosen state, by infrared or by Raman processes. This method allows us to select a given vibrational state in a well-defined rotational $J$ state.
Vibrational Excitation Hindering an Ion-Molecule Reaction: The c−C3H2+−H2 Collision Complex
2020
Experiments within a cryogenic 22-pole ion trap have revealed an interesting reaction dynamic phenomenon, where rovibrational excitation of an ionic molecule slows down a reaction with a neutral partner. This is demonstrated for the low-temperature hydrogen abstraction reaction $\mathrm{c}\text{\ensuremath{-}}{\mathrm{C}}_{3}{{\mathrm{H}}_{2}}^{+}+{\mathrm{H}}_{2}$, where excitation of the ion into the ${\ensuremath{\nu}}_{7}$ antisymmetric C-H stretching mode decreased the reaction rate coefficient toward the products $\mathrm{c}\text{\ensuremath{-}}{\mathrm{C}}_{3}{{\mathrm{H}}_{3}}^{+}+\mathrm{H}$. Supported by high-level quantum-chemical calculations, this observation is explained by th…
New ground state constants of 12CH335Cl and 12CH337Cl from global polyad analysis
2005
Abstract A global analysis of the infrared spectrum of chloromethane involving the ground state and the 13 vibrational states lying up to 2600 cm −1 was recently achieved using high resolution Fourier transform spectra of pure isotopomers. More than 20 000 transitions (cold and hot bands) for each isotopomer 12 CH 3 35 Cl and 12 CH 3 37 Cl have been assigned and fitted with a standard deviation of about 3 × 10 −4 cm −1 close to the experimental precison. As part of this global effort, improved ground state constants up to sextic centrifugal distortion terms have been determined for each isotopomer taking advantage of the numerous allowed and perturtation-allowed transitions simultaneously …
The distribution of the rotational transition strength in warm nuclei studied through γ-ray correlations
1995
Abstract The study of damping of rotational motion applying te rotational plane mapping (RPM) method is presented and discussed. The aim of this technique is to extract the distribution of the rotational transition strength from an analysis of the shape of the “central valley” of two- and three-dimensional γ-ray spectra. The method is applied to a triple γ-coincidence data set of 162,163Tm nuclei formed in 37Cl+130Te reactions. The rotational transition strength is obtained as a function of rotational frequency for selected regions of entry states, and the width is found to be rather constant and approximately equal to 80 keV. This value is significantly smaller than the value predicted the…
High-resolution spectroscopy and analysis of the stretching dyad of osmium tetroxide
2011
Abstract OsO4 is a heavy tetrahedral molecule that may constitute a benchmark for quantum chemistry calculations. Its favorable spin statistics (due to the zero nuclear spin of oxygen atoms) is such that only A1 and A2 rovibrational levels are allowed, leading to a dense, but quite easily resolved spectrum. Most lines are single ones, instead of complex line clusters as in the case of other heavy spherical-tops like SF6, for instance. It is thus possible to fully assign and fit the spectrum and to obtain precise experimental effective molecular parameters. The strong ν 3 stretching fundamental has been studied a long time ago as an isolated band [McDowell RS, Radziemski LJ, Flicker H, Galbr…
top data system ( TDS) software for infrared spectrum simulation of asymmetric molecules: some improvements to the TDS packages
2005
Abstract The spherical top data system (STDS) program suite developed in Dijon has been extended with the aim of studying any rovibrational band or polyad of XY 2 Z 2 ( C 2 v ) asymmetric top molecules. We work in the O ( 3 ) ⊃ T d ⊃ C 2 v chain because these species result from the substitution of two ligands of a corresponding “parent” spherical top and thus are relatively close to tetrahedral symmetry. The choice of this group chain has consequences on the method used to specify the input parameters of the programs for Hamiltonian and transition moment model calculations. One example concerning the ground state of the SO2F2 quasi-spherical molecule is presented. As before, this suite con…
C4v Top Data System (C4v TDS) software for infrared spectrum simulation of XY5Z symmetric molecules
2002
Abstract The Highly spherical Top Data System program suite developed in Dijon has been extended in the aim of studying any rovibrational band or polyad of XY5Z (C4v) symmetric top molecules. We work in the O(3)⊃Oh⊃C4v chain because most of these species result from the substitution of one ligand of the corresponding spherical tops and thus are relatively close to octahedral symmetry. The choice of this group chain has consequences in the way in which it is used to specify the input parameters of the programs for Hamiltonian and transition moment model calculations. One example concerning the ν1/ν8 dyad of the SF 5 35 Cl molecule is presented. As before, this suite consists of a series of F…
New assignments in the 2μm transparency window of the 12CH4 Octad band system
2013
Abstract This paper reports new assignments of rovibrational transitions of 12 CH 4 bands in the range 4600–4887 cm −1 which is usually referred to as a part of the 2 μm methane transparency window. Several experimental data sources for methane line positions and intensities were combined for this analysis. Three long path Fourier transform spectra newly recorded in Reims with 1603 m absorption path length and pressures of 1, 7 and 34 hPa for samples of natural abundance CH 4 provided new measurements of 12 CH 4 lines. Older spectra for 13 CH 4 (90% purity) from JPL with 73 m absorption path length were used to identify the corresponding lines. Most of the lines in this region belong to th…